CN115184335A - Raman detection method based on in-situ formation of coating layer on surface of nano gold particle induced by coagulation agent - Google Patents
Raman detection method based on in-situ formation of coating layer on surface of nano gold particle induced by coagulation agent Download PDFInfo
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Abstract
A Raman detection method based on a coagulation agent for inducing the surface of gold nanoparticles to form a coating in situ utilizes gold nanoparticle sol as an enhanced substrate, and different coagulation agents and precipitating agents are added to form the coating in situ on the surface of the gold particles, so that the detection capability of molecules such as crystal violet and the like is improved by 3-4 orders of magnitude. The method comprises the following steps: (1) Synthesizing an enhanced reagent gold nanoparticles, and synthesizing the gold nanoparticles by reducing chloroauric acid by using sodium citrate as a reducing agent. (2) Preparing dye molecule standard samples with different concentrations as a solution to be detected; putting a proper amount of gold nanoparticles and a solution to be detected into a sample cell, adding a certain amount of coagulation agent, and uniformly mixing; (3) Then adding a certain amount of precipitator into the sample pool and uniformly mixing, wherein the precipitator can react with the coagulation agent to generate insoluble substances, and a coating layer is formed on the surface of the gold particles; (4) And detecting the sample by using a portable Raman spectrometer.
Description
Technical Field
The invention belongs to the technical field of Raman spectrum detection, and particularly relates to a Raman detection method based on a coagulation agent for inducing the surface of a nano gold particle to form a coating layer in situ.
Background
The method is a convenient and rapid method for detecting molecules to be detected by using gold and silver nanoparticle sol as a reinforced substrate, and is very suitable for detecting liquid samples. The synthesis method of the gold nanoparticles is simple and is more stable than that of silver particles, however, in actual detection, the gold nanoparticles are used as the enhancement substrate, and high-sensitivity SERS detection is difficult to realize. In a sol system, molecules enter and exit and diffuse at a hot spot due to Brownian motion, and in addition, the molecules are adsorbed and desorbed on the surface of the nano particles, so that the molecules are difficult to fix at the hot spot on the surface of the particles, which causes that a stable signal with high sensitivity is difficult to detect by using the gold nano colloid as an enhanced substrate at a lower concentration.
The fixing and capturing of molecules to be detected on the surfaces of the nano particles are beneficial to improving the detection performance of the molecules, the existing research of Raman detection by a sol method mainly focuses on the optimization of the types and the addition amount of the coagulation agents, and hot spots are generated by the aggregation of the nano particles. And researches on how to further fix the molecules to be detected at the hot spot of the nano particles so as to improve the detection sensitivity are relatively reduced. Therefore, by adding the coagulation agent, a new method is developed in a system in which the gold nanoparticle sol is used as a reinforcing agent, and the method has important research significance and application prospect for improving the detection capability of the molecules.
Disclosure of Invention
The invention aims to provide a Raman detection method for improving the detection capability of molecules to be detected by using gold nanoparticle sol as an enhanced substrate and adding different coagulation agents and precipitating agents to form a coating layer on the surface of a gold particle in situ and inducing the surface of the gold nanoparticle to form the coating layer based on the coagulation agents.
In order to achieve the purpose, the technical scheme of the invention is as follows:
step 1, preparing gold nanoparticles:
adding 100mL of ultrapure water into a conical flask, stirring and heating to 130 ℃, adding 3-5mL of 1-2% by mass sodium citrate aqueous solution, uniformly mixing, adding 0.25-0.35mL of 10-25mmol/L chloroauric acid solution, and continuously reacting to obtain a nanogold seed solution;
growing the nano-gold in the second step: adding 160mL of ultrapure water and 40mL of nano-gold seed solution into a conical flask, stirring and heating to 130 ℃, adding 3-5mL of 1-2% by mass sodium citrate aqueous solution, uniformly mixing, adding 10-25mmol/L chloroauric acid solution, adding 0.4mL of chloroauric acid solution each time, adding 10 times at an interval of 8 minutes each time, adding chloroauric acid at the last time, and continuing to react for 15 minutes to obtain nano-gold solution grown in the second step;
the third step is growth: adding 160mL of ultrapure water and 40mL of the nanogold solution obtained by the second-step growth into a conical flask, stirring and heating to 130 ℃, adding 3-5mL of sodium citrate aqueous solution with the mass fraction of 1-2%, uniformly mixing, adding 10-25mmol/L chloroauric acid solution, adding 0.4mL of chloroauric acid solution every time, adding 10 times at intervals of 8 minutes every time, and continuing to react for 15 minutes after adding chloroauric acid for the last time to obtain the final gold nanoparticle sol;
step 2, preparing the molecular standard solutions to be detected with different concentrations
Adding 250-500uL of gold nanoparticle sol into a sample detection pool, adding 1-2mL of dye molecule standard solution to be detected, mixing uniformly, adding 10-250uL of coagulation agent with the concentration of 1-2mol/L, mixing uniformly, adding 2-250uL of precipitator with the concentration of 10mmol/L-1.5mol/L, and detecting the sample by using a portable Raman spectrometer after mixing uniformly.
The coagulation agent is sodium chloride, sodium bromide, sodium iodide, calcium chloride or magnesium sulfate.
The precipitant is silver nitrate, magnesium sulfate or sodium carbonate.
The coagulation agent and the precipitator can react to generate insoluble or indissolvable compounds, and when the coagulation agent is sodium chloride, sodium bromide or sodium iodide, the precipitator is silver nitrate; when the coagulating agent is calcium chloride, the precipitating agent is silver nitrate, magnesium sulfate or sodium carbonate; when the coagulating agent is magnesium sulfate, the precipitating agent is silver nitrate.
The dye molecules in the dye molecule standard solution comprise: crystal violet, rhodamine 6G, diquat, methylene blue or malachite green.
The volume of the gold nanoparticle sol in the step 2 is 250uL.
And the volume of the dye molecule standard solution to be detected in the step 2 is 1mL.
The concentration of the coagulation agent in the step 2 is 1.5mol/L.
Compared with the prior art, the invention has the beneficial effects that:
1. the gold nanoparticle sol, the dye molecule solution to be detected and the coagulation agent are added into a sample detection pool and then mixed uniformly, then a precipitator which can react with the coagulation agent to generate insoluble precipitate is added, and the surface of the gold nanoparticle is covered with the precipitator to form a coating layer. The coating layer enables molecules to be detected to be fixed at a hot spot, and detection signals are improved.
2. According to the invention, the coating layer is generated on the surface of the gold nanoparticle through the reaction between the coagulation agent and the precipitating agent, the reaction is rapid, the response signal of the molecule to be detected can be rapidly generated, and the method has the advantages of various selections of the coagulation agent and the precipitating agent and high flexibility.
3. According to the invention, after the coagulation agent and the precipitating agent are added, coating layers are generated on the surfaces of the gold particles, so that the detection sensitivity of the molecules to be detected is improved, and compared with a sample without the precipitating agent, the detection capability is improved by 3-4 orders of magnitude. The method is simple to operate and high in repeatability, and the detection sensitivity and application prospect of the gold nanoparticle sol as the enhanced substrate are improved.
Drawings
FIG. 1 is a transmission electron microscope image of gold nanoparticle sol after adding sodium chloride coagulation agent;
FIG. 2 is a transmission electron microscope image of gold nanoparticle sol after adding sodium chloride coagulation agent and silver nitrate precipitation agent;
FIG. 3 is a Raman spectrum of a gold nanoparticle sol added with a sodium chloride coagulation agent to detect crystal violet samples of different concentrations;
FIG. 4 is a Raman spectrum of a crystal violet sample with different concentrations detected by adding a sodium chloride coagulation agent and a silver nitrate precipitation agent into gold nanoparticle sol;
FIG. 5 is a Raman spectrum of a gold nanoparticle sol added with a sodium chloride coagulation agent and a silver nitrate precipitation agent to detect rhodamine 6G samples with different concentrations;
FIG. 6 is a Raman spectrum of gold nanoparticle sol added with sodium chloride coagulation agent and silver nitrate precipitant to detect diquat in different concentrations;
FIG. 7 is a Raman spectrum of a crystal violet sample with different concentrations detected by adding a calcium chloride coagulation agent and a magnesium sulfate precipitation agent to gold nanoparticle sol;
FIG. 8 is a Raman spectrum of a crystal violet sample with different concentrations detected by adding a magnesium sulfate coagulation agent and a silver nitrate precipitation agent into gold nanoparticle sol.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings.
Example 1:
step 1, preparing gold nanoparticles:
adding 100mL of ultrapure water into a conical flask, stirring and heating to 130 ℃, adding 4mL of 1% by mass sodium citrate aqueous solution, uniformly mixing, adding 0.3mL of 10mmol/L chloroauric acid solution, and continuously reacting to obtain a nanogold seed solution;
growing the nano-gold in the second step: adding 160mL of ultrapure water and 40mL of nanogold seed solution into a conical flask, stirring and heating to 130 ℃, adding 4mL of sodium citrate aqueous solution with the mass fraction of 1%, uniformly mixing, adding 0.4mL of chloroauric acid solution with the concentration of 10mmol/L each time, adding 10 times at an interval of 8 minutes each time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the nanogold solution grown in the second step;
and a third step of growth: adding 160mL of ultrapure water and 40mL of the nano-gold solution obtained by the second-step growth into a conical flask, stirring and heating to 130 ℃, adding 4mL of sodium citrate aqueous solution with the mass fraction of 1%, uniformly mixing, adding 0.4mL of chloroauric acid solution with the concentration of 10mmol/L, adding 10 times, each time at an interval of 8 minutes, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the final gold nanoparticle sol;
step 2, preparing the molecular standard solutions to be detected with different concentrations
Preparing 0.01mol/L crystal violet standard solution, and sequentially diluting the solution to obtain 10 -8 mol/L-10 -14 And (4) mol/L of standard solution to be detected. Adding 250uL of gold nanoparticle sol into a sample detection pool, adding 1mL of dye molecule crystal violet standard solution to be detected, mixing uniformly, adding 250uL of sodium chloride coagulation agent with the concentration of 1.5mol/L, and mixing uniformly to enable the nanoparticles to generate aggregation. Detecting the sample by using a portable Raman spectrometer with the power of 300mW, the laser wavelength of 785nm and the productThe time is divided into 20s.
And then adding 10uL of silver nitrate precipitating agent with the concentration of 10mmol/L, uniformly mixing, and detecting the sample by using the portable Raman spectrometer again, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
As can be seen from fig. 1, nanoparticles without precipitant are aggregated and the dispersed nanoparticles are close together. It can be seen from fig. 2 that after adding the precipitating agent, a precipitation layer is formed on the surface of the particles, and the adjacent nanoparticles are connected by the precipitation layer and are no longer dispersed single particles.
In example 1, the raman spectra of crystal violet samples with different concentrations after being added with sodium chloride coagulating agent are shown in fig. 3, and the concentration of 10 can be detected -8 The crystal violet signal of mol/L when the concentration of the liquid to be detected is 10 -9 At mol/L, no detection signal can be obtained.
In example 1, the raman spectra of the crystal violet samples with different concentrations after adding the sodium chloride coagulating agent and the silver nitrate precipitating agent are shown in fig. 4, and the detected concentration is 10 -12 Compared with the sample without the precipitant in the example 1, the detection sensitivity of the crystal violet signal of mol/L is improved by 4 orders of magnitude.
Example 2:
step 1, preparing gold nanoparticles:
adding 100mL of ultrapure water into a conical flask, stirring and heating to 130 ℃, adding 3mL of sodium citrate aqueous solution with the mass fraction of 1.3%, uniformly mixing, adding 0.32mL of chloroauric acid solution with the concentration of 18mmol/L, and continuously reacting to obtain a nanogold seed solution;
growing the nano gold in the second step: adding 160mL of ultrapure water and 40mL of nanogold seed solution into a conical flask, stirring and heating to 130 ℃, adding 3mL of sodium citrate aqueous solution with the mass fraction of 1.3%, uniformly mixing, adding 0.4mL of chloroauric acid solution with the concentration of 18mmol/L, adding 10 times of chloroauric acid solution with the interval of 8 minutes each time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the nanogold solution grown in the second step;
the third step is growth: adding 160mL of ultrapure water and 40mL of the nano gold solution obtained by the second growth into a conical flask, stirring and heating to 130 ℃, adding 3mL of a sodium citrate aqueous solution with the mass fraction of 1.3%, uniformly mixing, then adding a chloroauric acid solution with the concentration of 18mmol/L, adding 0.4mL of chloroauric acid every time for 10 times at an interval of 8 minutes every time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the final gold nanoparticle sol;
step 2, preparing the molecular standard solution to be detected with different concentrations
Preparing 0.01mol/L rhodamine 6G standard solution, and sequentially diluting the solution to obtain 10 -8 mol/L-10 -13 And (4) mol/L of standard solution to be detected. Adding 300uL of gold nanoparticle sol into a sample detection pool, adding 1.5mL of dye molecule rhodamine 6G standard solution to be detected, uniformly mixing, adding 200uL of sodium chloride coagulation agent with the concentration of 1.2mol/L, and uniformly mixing to enable nanoparticles to generate aggregation. And (3) detecting the sample by using a portable Raman spectrometer, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
And then adding 100uL of silver nitrate precipitating agent with the concentration of 100mmol/L, uniformly mixing, and detecting the sample by using the portable Raman spectrometer again, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
In example 2, the raman spectra of rhodamine 6G samples with different concentrations detected by adding sodium chloride coagulating agent and silver nitrate precipitating agent are shown in fig. 5. No 10 could be detected without adding silver nitrate precipitant -9 Raman signals of mol/L rhodamine 6G; after adding the silver nitrate precipitator, the lowest detectable 10 -12 mol/L。
Example 3:
step 1, preparing gold nanoparticles:
adding 100mL of ultrapure water into a conical flask, stirring and heating to 130 ℃, adding 5mL of sodium citrate aqueous solution with the mass fraction of 1.8%, uniformly mixing, adding 0.28mL of chloroauric acid solution with the concentration of 25mmol/L, and continuously reacting to obtain a nanogold seed solution;
growing the nano-gold in the second step: adding 160mL of ultrapure water and 40mL of nanogold seed solution into a conical flask, stirring and heating to 130 ℃, adding 5mL of 2% by mass sodium citrate aqueous solution, uniformly mixing, adding 0.4mL of chloroauric acid solution with the concentration of 13mmol/L, adding 10 times at an interval of 8 minutes each time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the nanogold solution grown in the second step;
and a third step of growth: adding 160mL of ultrapure water and 40mL of the nano gold solution obtained by the second growth into a conical flask, stirring and heating to 130 ℃, adding 5mL of 2% by mass sodium citrate aqueous solution, uniformly mixing, adding 0.4mL of chloroauric acid solution with the concentration of 25mmol/L, adding 10 times at intervals of 8 minutes, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the final gold nanoparticle sol;
step 2, preparing the molecular standard solutions to be detected with different concentrations
Preparing 0.01mol/L aquacide standard solution, and sequentially diluting the solution to obtain 10 -7 mol/L-10 -10 And (4) mol/L of standard solution to be detected. Adding 400uL of gold nanoparticle sol into a sample detection pool, adding 1.8mL of standard solution of dye molecule to be detected diquat, mixing uniformly, and adding 100uL of sodium chloride coagulating agent with the concentration of 1mol/L, mixing uniformly to enable the nanoparticles to generate aggregation. And detecting the sample by using a portable Raman spectrometer, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
And then adding 2uL of silver nitrate precipitant with the concentration of 500mmol/L, uniformly mixing, and detecting the sample by using the portable Raman spectrometer, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
In example 3, raman spectra of samples of diquat at different concentrations with the addition of sodium chloride coagulating agent and silver nitrate precipitating agent are shown in fig. 6. No 10 could be detected without adding silver nitrate precipitant -8 Raman signals of mol/L diquat; after adding the silver nitrate precipitator, the lowest detectable 10 can be obtained -9 mol/L。
Example 4:
step 1, preparing gold nanoparticles:
adding 100mL of ultrapure water into a conical flask, stirring and heating to 130 ℃, adding 3.5mL of 2% by mass sodium citrate aqueous solution, uniformly mixing, adding 0.35mL of 13mmol/L chloroauric acid solution, and continuously reacting to obtain a nanogold seed solution;
growing the nano-gold in the second step: adding 160mL of ultrapure water and 40mL of nanogold seed solution into a conical flask, stirring and heating to 130 ℃, adding 4.5mL of sodium citrate aqueous solution with the mass fraction of 1.5%, uniformly mixing, adding 20mmol/L chloroauric acid solution, adding 0.4mL of chloroauric acid solution each time, adding 10 times at an interval of 8 minutes each time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the nanogold solution grown in the second step;
the third step is growth: adding 160mL of ultrapure water and 40mL of the nano-gold solution obtained by the second-step growth into a conical flask, stirring and heating to 130 ℃, adding 4.5mL of a sodium citrate aqueous solution with the mass fraction of 1.5%, uniformly mixing, adding a chloroauric acid solution with the concentration of 13mmol/L, adding 0.4mL of the chloroauric acid solution for 10 times each time at an interval of 8 minutes each time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the final gold nanoparticle sol;
step 2, preparing the molecular standard solutions to be detected with different concentrations
Preparing 0.01mol/L crystal violet standard solution, and sequentially diluting the solution to obtain 10 -8 mol/L-10 -13 And (4) mol/L of standard solution to be detected. Adding 500uL of gold nanoparticle sol into a sample detection pool, adding 1.5mL of dye molecule crystal violet standard solution to be detected, mixing uniformly, adding 50uL of calcium chloride coagulation agent with the concentration of 2mol/L, and mixing uniformly to enable nanoparticles to generate aggregation. And (3) detecting the sample by using a portable Raman spectrometer, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
And then adding 200uL of magnesium sulfate precipitator with the concentration of 1mol/L, uniformly mixing, and detecting the sample by using the portable Raman spectrometer again, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
In example 4, the raman spectra of different concentrations of crystal violet samples tested with the addition of calcium chloride coagulant and magnesium sulfate precipitant are shown in fig. 7. Without addingIn the case of magnesium sulfate precipitant, 10 was not detected -9 Raman signal of mol/L crystal violet; after addition of magnesium sulfate precipitant, a minimum of 10 could be detected -11 mol/L。
Example 5:
step 1, preparing gold nanoparticles:
adding 100mL of ultrapure water into a conical flask, stirring and heating to 130 ℃, adding 4.5mL of sodium citrate aqueous solution with the mass fraction of 1.5%, uniformly mixing, adding 0.25mL of 20mmol/L chloroauric acid solution, and continuously reacting to obtain a nanogold seed solution;
growing the nano gold in the second step: adding 160mL of ultrapure water and 40mL of nanogold seed solution into a conical flask, stirring and heating to 130 ℃, adding 3.5mL of sodium citrate aqueous solution with the mass fraction of 1.8%, uniformly mixing, adding 25mmol/L chloroauric acid solution, adding 0.4mL of chloroauric acid solution each time, adding 10 times at an interval of 8 minutes each time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the nanogold solution grown in the second step;
and a third step of growth: adding 160mL of ultrapure water and 40mL of the nano-gold solution obtained by the second-step growth into a conical flask, stirring and heating to 130 ℃, adding 3.5mL of a sodium citrate aqueous solution with the mass fraction of 1.8%, uniformly mixing, adding a chloroauric acid solution with the concentration of 20mmol/L, adding 0.4mL of the chloroauric acid solution for 10 times each time at an interval of 8 minutes each time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the final gold nanoparticle sol;
step 2, preparing the molecular standard solutions to be detected with different concentrations
Preparing 0.01mol/L crystal violet standard solution, and sequentially diluting the solution to obtain 10 -8 mol/L-10 -13 And (4) mol/L of standard solution to be detected. Adding 450uL of gold nanoparticle sol into a sample detection pool, adding 2mL of dye molecule crystal violet standard solution to be detected, mixing uniformly, adding 10uL of magnesium sulfate coagulation agent with the concentration of 1.8mol/L, and mixing uniformly to enable nanoparticles to generate aggregation. And (3) detecting the sample by using a portable Raman spectrometer, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
And then adding 250uL of silver nitrate precipitant with the concentration of 1.5mol/L, uniformly mixing, and detecting the sample by using the portable Raman spectrometer, wherein the power of the Raman spectrometer is 300mW, the laser wavelength is 785nm, and the integration time is 20s.
In example 5, raman spectra of samples of crystal violet of different concentrations tested with the addition of magnesium sulfate coagulating agent and silver nitrate precipitating agent are shown in fig. 8. No 10 could be detected without adding silver nitrate precipitant -9 Raman signal of mol/L crystal violet; after adding the silver nitrate precipitator, the lowest detectable 10 -11 mol/L。
Claims (8)
1. A Raman detection method based on gold nanoparticle surface in-situ coating layer formation induced by coagulation agent is characterized by comprising the following steps:
step 1, preparing gold nanoparticles:
adding 100mL of ultrapure water into a conical flask, stirring and heating to 130 ℃, adding 3-5mL of 1-2% by mass of sodium citrate aqueous solution, uniformly mixing, adding 0.25-0.35mL of 10-25mmol/L chloroauric acid solution, and continuously reacting to obtain a nanogold seed solution;
growing the nano-gold in the second step: adding 160mL of ultrapure water and 40mL of nanogold seed solution into a conical flask, stirring and heating to 130 ℃, adding 3-5mL of sodium citrate aqueous solution with the mass fraction of 1-2%, uniformly mixing, adding 10-25mmol/L chloroauric acid solution, adding 0.4mL of chloroauric acid solution every time, adding 10 times at an interval of 8 minutes every time, adding chloroauric acid for the last time, and continuing to react for 15 minutes to obtain the nanogold solution grown in the second step;
the third step is growth: adding 160mL of ultrapure water and 40mL of the nanogold solution obtained by the second-step growth into a conical flask, stirring and heating to 130 ℃, adding 3-5mL of sodium citrate aqueous solution with the mass fraction of 1-2%, uniformly mixing, adding 10-25mmol/L chloroauric acid solution, adding 0.4mL of chloroauric acid solution every time, adding 10 times at intervals of 8 minutes every time, and continuing to react for 15 minutes after adding chloroauric acid for the last time to obtain the final gold nanoparticle sol;
step 2, preparing the molecular standard solutions to be detected with different concentrations
Adding 250-500uL of gold nanoparticle sol into a sample detection pool, adding 1-2mL of dye molecule standard solution to be detected, mixing uniformly, adding 10-250uL of coagulation agent with the concentration of 1-2mol/L, mixing uniformly, adding 2-250uL of precipitator with the concentration of 10mmol/L-1.5mol/L, and detecting the sample by using a portable Raman spectrometer after mixing uniformly.
2. The method for Raman detection according to claim 1, wherein the coagulating agent is sodium chloride, sodium bromide, sodium iodide, calcium chloride or magnesium sulfate.
3. The method for Raman detection based on the in-situ formation of the coating layer on the surface of the gold nanoparticle induced by the coagulation agent as claimed in claim 1, wherein the precipitation agent is silver nitrate, magnesium sulfate, or sodium carbonate.
4. The method for Raman detection based on the in-situ formation of the coating layer on the surface of the gold nanoparticle induced by the coagulation agent according to claims 2 and 3, wherein the coagulation agent and the precipitating agent react to generate an insoluble or slightly soluble compound, and when the coagulation agent is sodium chloride, sodium bromide or sodium iodide, the precipitating agent is silver nitrate; when the coagulating agent is calcium chloride, the precipitating agent is silver nitrate, magnesium sulfate or sodium carbonate; when the coagulating agent is magnesium sulfate, the precipitating agent is silver nitrate.
5. The method for Raman detection based on the in-situ formation of the coating layer on the surface of the gold nanoparticle induced by the coagulation agent as claimed in claim 1, wherein the dye molecules in the standard solution of the dye molecules comprise: crystal violet, rhodamine 6G, diquat, methylene blue or malachite green.
6. The method for Raman detection according to claim 1, wherein the volume of the gold nanoparticle sol in step 2 is 250uL.
7. The method for Raman detection based on the in-situ formation of the coating layer on the surface of the gold nanoparticle induced by the coagulation agent as claimed in claim 1, wherein the volume of the dye molecule standard solution to be detected in step 2 is 1mL.
8. The method for Raman detection according to claim 1, wherein the concentration of the coagulation agent in step 2 is 1.5mol/L.
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